Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale

ABSTRACT

A composition includes an anionic polysaccharide hybrid polymer composition and 2-phosphonobutane-1,2,4-tricarboxylic acid. In one embodiment, the polysaccharide hybrid polymer composition includes a polysaccharide residue present in an amount from approximately 5% to approximately 90% by weight of the polysaccharide hybrid polymer composition and a residue of at least one ethylenically unsaturated monomer present in an amount from approximately 10% to approximately 75% by weight of the polysaccharide hybrid polymer composition.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part application of U.S.application Ser. No. 13/204,368 that was filed with the United StatesPatent and Trademark Office on Aug. 5, 2011, which application isincorporated by reference in its entirety herein.

TECHNICAL FIELD

The present invention is related to the field of hard water scalecontrol. In particular, the present invention is related to a cleaningcomposition including a polysaccharide hybrid polymer composition and2-phosphonobutane-1,2,4-tricarboxylic acid or salts thereof for hardwater scale control, particularly in a high alkaline environment.

BACKGROUND

Conventional detergents used in food and beverage (e.g., the dairy,cheese, sugar, meat, food, and brewery and other beverage industries),warewashing and laundry industries include alkaline detergents. Alkalinedetergents, particularly those intended for institutional and commercialuse, generally contain phosphates, nitrilotriacetic acid (NTA) andethylenediaminetetraacetic acid (EDTA). Phosphates, NTA and EDTA arecomponents commonly used in detergents to remove soils and to sequestermetal ions such as calcium, magnesium and iron.

In particular, NTA, EDTA or polyphosphates such as sodiumtripolyphosphate and their salts are used in detergents because of theirability to solubilize preexisting inorganic salts and/or soils. Whencalcium, magnesium and iron salts precipitate, the crystals may attachto the surface being cleaned and cause undesirable effects. For example,calcium carbonate precipitation on the surface of ware can negativelyimpact the aesthetic appearance of the ware, giving an unclean look. Inthe laundering area, if calcium carbonate precipitates and attaches ontothe surface of fabric, the crystals may leave the fabric feeling hardand rough to the touch. In the food and beverage industry, the calciumcarbonate residue can affect the acidity levels of foods. The ability ofNTA, EDTA and polyphosphates to remove metal ions facilitates thedetergency of the solution by preventing hardness precipitation,assisting in soil removal and/or preventing soil redeposition into thewash solution or wash water.

While effective, phosphates and NTA are subject to governmentregulations due to environmental and health concerns. Although EDTA isnot currently regulated, it is believed that government regulations maybe implemented due to environmental persistence. Therefore, there is aneed in the art for an alternative, and preferably environment friendly,cleaning composition that can replace the properties ofphosphorous-containing compounds such as phosphates, phosphonates,phosphites, and acrylic phosphinate polymers, as well asnon-biodegradable aminocarboxylates such as NTA and EDTA.

SUMMARY

The present invention includes a cleaning composition for controllinghard water scale accumulation. The composition includes a polysaccharidehybrid polymer composition and 2-phosphonobutane-1,2,4-tricarboxylicacid. In some embodiments, the polysaccharide hybrid polymer compositionincludes a polysaccharide residue present in an amount from about 5% toabout 90% by weight of the polysaccharide hybrid polymer composition anda residue of at least one ethylenically unsaturated monomer present inan amount from about 10% to about 75% by weight of the polysaccharidehybrid polymer composition.

In other embodiments, the cleaning composition is used by mixing waterwith the composition to form a use solution. The water and compositioncan be mixed so that the use solution has a polysaccharide hybridpolymer composition concentration from about 1 part-per-million (ppm) toabout 500 ppm.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram related to a 100 cycle warewashing test.

DETAILED DESCRIPTION

The present cleaning compositions include a polysaccharide hybridpolymer composition and 2-phosphonobutane-1,2,4-tricarboxylic acid orsalts thereof (PBTC). Such compositions may be useful in controllinghard water scale, particularly in water treatment applications and inhigh alkaline environments. Further, such compositions can bebiodegradable and substantially free of phosphorous containingcomponents to comply with various regulatory requirements.

The present compositions can be used in any environment in which it isdesirable to control hard water scale and to remove or preventredeposition of soil, such as protein, on surfaces such as but notlimited to plastic, glass, ceramic and metal. Example applicationsinclude warewashing, laundering, institutional, health care, food andbeverage, and water treatment applications. More particularly, exampleapplications include, but are not limited to: machine and manualwarewashing, presoaks, laundry and textile cleaning and destaining,carpet cleaning and destaining, surface cleaning and destaining, kitchenand bath cleaning and destaining, floor cleaning and destaining,cleaning in place operations, general purpose cleaning and destaining,industrial or household cleaners, and industrial or municipal watersystems. The present compositions may also be used as textile scours,mineral deposition, or in oilfield applications, such as for scaleinhibition or drilling aids. Methods of using the composition are alsoprovided.

The cleaning compositions generally include a polysaccharide hybridpolymer composition, and 2-phosphonobutane-1,2,4-tricarboxylic acid orsalts thereof (PBTC). Suitable weight ratios of polysaccharide hybridpolymer composition to PBTC are from about 15:1 to about 1:15.Particularly suitable weight ratios of polysaccharide hybrid polymercomposition to PBTC are from about 10:1 to about 1:10. In an embodiment,the polysaccharide hybrid polymer composition is anionic polysaccharidehybrid polymer composition. In another embodiment, the polysaccharidehybrid polymer composition is a copolymer.

The polysaccharide hybrid polymer compositions of the present inventionare produced by polymerizing with free radical initiators at least oneethylenically unsaturated monomer in the presence of the polysaccharideas a chain transfer agent, such as described in U.S. Pat. No. 7,666,963and PCT Publication No. WO 2011/014783, each of which is incorporated byreference in its entirety herein. The polymerization is initiated by anon-metal or a non-metal ion initiator, such as inorganic peroxidesincluding, but not limited to, hydrogen peroxide, sodium persulfate,potassium persulfate and ammonium persulfate.

As described herein, a “hybrid polymer composition” is a mixture of (a)a hybrid synthetic polymer and (b) a hybrid polymer. The hybrid polymercompositions of the present invention thus contain at least the twomoieties, (a) and (b), with a minimum amount of the hybrid syntheticpolymer (a) since this component generates the chain transfer whichleads to the formation of the hybrid polymer (b). One skilled in the artwill recognize that the hybrid polymer composition may contain a certainamount of the unreacted naturally derived hydroxyl containing chaintransfer agent. Suitable hybrid polymer compositions are described inPCT Publication No. WO 2011/014783. The term “hybrid polymer”, asdefined herein, refers to a polymer of ethylenically unsaturatedmonomers with an end group containing the naturally derived hydroxylcontaining chain transfer agent which is a result of the hybridsynthetic polymer chain transfer. Also as used herein, the term “hybridsynthetic polymer” is a synthetic polymer derived from syntheticmonomers with a hybrid initiator fragment as one end group. The otherend group is a proton resulting from chain transfer to the naturallyderived hydroxyl containing chain transfer agent. As used herein, theterm “synthetic monomer” means any ethylenically unsaturated monomerwhich can undergo free radical polymerization. In some embodiments, thehybrid polymer composition suitable for use in this invention is ananionic hybrid polymer or copolymer composition.

Polymerization may change a component from its original structure to aderivative structure. As used herein, the term “residue” refers to thestarting component or anything derived from the component duringpolymerization which is part of the polymer. For example, a residue ofacrylic acid includes acrylic acid and anything derived from acrylicacid during polymerization which is part of the polymer or resultingpolymer composition. In one example, the polysaccharide hybrid polymercomposition can have a weight average molecular weight from about 2,000g/mol to about 25,000 g/mol. In another embodiment, the polysaccharidehybrid polymer composition has a weight average molecular weight fromabout 5,000 g/mol to about 20,000 g/mol and in yet another embodimentsfrom about 7,000 to about 15,000 g/mol. The weight average molecularweight may be determined by several methods, with Gel PermeationChromotagraphy (GPC) using the appropriate methods and standards as thepreferred method.

The residue of a polysaccharide includes a polysaccharide and anythingderived from the polysaccharide during polymerization which is part ofthe polysaccharide hybrid polymer. Suitable polysaccharides can bederived from plant, animal and microbial sources. Examplepolysaccharides include but are not limited to maltodextrins, starches,cellulose, gums (e.g., gum arabic, guar and xanthan), alginates, pectinand gellan. Suitable starches include those derived from maize, potato,tapioca, wheat, rice, pea, sago, oat, barley, rye, and amaranth,including conventional hybrids or genetically engineered materials.Additional example polysaccharides include hemicellulose or plant cellwall polysaccharides such as D-xylans.

The polysaccharides can be modified or derivatized by etherification(e.g., via treatment with propylene oxide, ethylene oxide,2,3-epoxypropyltrimethylammonium chloride), esterification (e.g., viareaction with acetic anhydride, octenyl succinic anhydride (‘OSA’)),acid hydrolysis, dextrinization, oxidation or enzyme treatment (e.g.,starch modified with α-amylase, β-amylase, pullanase, isoamylase orglucoamylase), or various combinations of these treatments.

The polysaccharide hybrid polymer composition also includes residue ofat least one ethylenically unsaturated monomer. In some embodiments, theat least one ethylenically unsaturated monomer is an anionicethylenically unsaturated monomer. Examples of anionic ethylenicallyunsaturated monomers include but are not limited to acrylic acid,methacrylic acid, ethacrylic acid, α-chloro-acrylic acid, α-cyanoacrylic acid, β-methyl-acrylic acid (crotonic acid), α-phenyl acrylicacid, β-acryloxy propionic acid, sorbic acid, α-chloro sorbic acid,angelic acid, cinnamic acid, p-chloro cinnamic acid, β-styryl acrylicacid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid,citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaricacid, tricarboxy ethylene, 2-acryloxypropionic acid,2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodiummethallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acidand maleic acid. The anionic ethylenically unsaturated monomers mayinclude half esters of maleic and itaconic acid such as monomethyl,monoethyl, monopropyl, monobutyl, monoisopropyl and monotertbutylmaleate, and monomethyl, monoethyl, monopropyl, monobutyl, monoisopropyland monotertbutyl itaconate. Moieties such as maleic anhydride oracrylamide that can be derivatized to an acid containing group can beused. Combinations of anionic ethylenically unsaturated monomers canalso be used. In an embodiment, the anionic ethylenically unsaturatedmonomers include acrylic acid, maleic acid, methacrylic acid,2-acrylamido-2-methyl propane sulfonic acid, monomethyl maleate and/ormixtures thereof or their salts. In another embodiment, theacid-containing monomers are acrylic acid and/or methacrylic acid. As anexample, the anionic polysaccharide hybrid polymer composition includesacrylic acid residue. The residue of acrylic and methacrylic acid may bederived from acrylic and methacrylic acid monomers or may be generatedfrom a hydrolyzable monomer. For example, a methacrylic acid residue maybe partially or completely hydrolyzed from methyl methacrylate. Theresidues of acrylic acid and methacrylic acid may also be present aslithium, sodium, and potassium salts, ammonium and amine salts.

The polysaccharide hybrid polymer composition may optionally includeresidue of other ethylenically unsaturated monomers. In an embodiment,such other ethylenically unsaturated monomers are hydrophilic. Examplesof other ethylenically unsaturated monomers include but are not limitedto hydroxyalkyl(meth)acrylate or dialkyl maleate or dialkyl itaconate. Aresidue of hydroxyalkyl(meth)acrylate includes both hydroxyalkylacrylate and hydroxyalkyl methacrylate. Examples of suitablehydroxyalkyl(meth)acrylates include but are not limited tohydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl,hydroxyisopropyl and hydroxytertbutyl(meth)acrylates. Suitable dialkylmaleates include but are not limited to diethyl, dipropyl, dibutyl,diisopropyl and ditertbutyl maleate. Suitable dialkyl itaconates includebut are not limited monomethyl, monoethyl, monopropyl, monobutyl,monoisopropyl and monotertbutyl itaconate. The polysaccharide hybridpolymer composition may optionally include residue of more than oneethylenically unsaturated monomer. In an embodiment, the polysaccharidehybrid polymer composition includes residue of two ethylenicallyunsaturated monomers present in the polysaccharide hybrid polymercomposition in weight ratios from about 1:5 to about 5:1. In a preferredembodiment, acrylic acid and maleic acid are present in thepolysaccharide hybrid polymer composition in weight ratios from about1:5 to about 5:1.

A suitable concentration range of the components in the polysaccharidehybrid polymer composition include from about 5% to about 90% by weightpolysaccharide residue and from about 10% to about 75% by weight residueof at least one ethylenically unsaturated monomer. In anotherembodiment, the polysaccharide hybrid polymer composition include fromabout 30% to about 80% by weight polysaccharide residue. A particularlysuitable concentration range of the components in the polysaccharidehybrid polymer composition includes from about 40% to about 70% byweight polysaccharide residue and from about 5% to about 50% by weightresidue of the at least one ethylenically unsaturated monomer. Thecomponent weight percentages of the polysaccharide hybrid polymercomposition given above and in the examples are based on the amounts ofthe respective ingredients as originally added to the polysaccharidehybrid polymer composition. One skilled in the art will recognize thatthe weight percent of each component in the final polysaccharide hybridpolymer composition may vary due to the polymerization process.

The composition also includes phosphonobutane-1,2,4-tricarboxylic acidor salts thereof (PBTC). Suitable commercially available PBTC includeBayhibit S a 2-phosphobutane-1,2,4-tricarboxylic acid tetrasodium saltavailable from Lanxess, Pittsburgh, Pa. The combination ofpolysaccharide hybrid polymer composition and PBTC may effectivelycontrol hard water scale accumulation.

In another embodiment the composition is a detergent composition thatgenerally includes an alkali metal hydroxide, water, a polysaccharidehybrid polymer composition, and 2-phosphonobutane-1,2,4-tricarboxylicacid or salts thereof (PBTC). The detergent composition, for example,may be particularly suitable for removing soil from a substrate,preventing soil redeposition and controlling hard water scale. Asuitable concentration range of the components in a concentrated form ofthe detergent compositions include from about 1% to about 80% by weightalkali metal hydroxide, from about I to about 40% by weight of water,from about 0.1% to about 15% by weight of the polysaccharide hybridpolymer composition, and from about 0.01% to about 10% by weight ofPBTC. A particularly suitable concentration range of the components inthe detergent compositions include from about 20% to about 70% by weightalkali metal hydroxide, from about 5% to about 30% by weight of water,from about 1% to about 10% by weight of the polysaccharide hybridpolymer composition, and from about 0.5% to about 10% by weight of PBTC.

Suitable alkali metal hydroxides include but are not limited to: sodiumhydroxide, potassium hydroxide, lithium hydroxide, and combinationsthereof. The alkali metal hydroxide may be added to the composition inany form known in the art, including as solid beads, dissolved in anaqueous solution, or a combination thereof. Additionally, more than onealkalinity source may be used according to certain embodiments.

The alkali metal hydroxide controls the pH of the resulting solutionwhen water is added to the detergent composition to form a use solution.The pH of the use solution must be maintained in the alkaline range inorder to provide sufficient detergency properties. In one embodiment,the pH of the use solution is from approximately 9 to approximately 13.Particularly, the pH of the use solution is from about 10 to about 12.If the pH of the use solution is too high, for example, above about 13,the use solution may be too alkaline and attack or damage the surface tobe cleaned.

The alkali metal hydroxide may also function as a hydratable salt toform a solid composition. The hydratable salt can be referred to assubstantially anhydrous. By substantially anhydrous, it is meant thatthe component contains less than about 2% by weight water based upon theweight of the hydratable component. The amount of water can be less thanabout 1% by weight, and can be less than about 0.5% by weight. There isno requirement that the hydratable salt be completely anhydrous.

The detergent composition also includes water of hydration to hydratethe alkali metal hydroxide/hydratable salt. It should be understood thatthe reference to water includes both water of hydration and free water.The phrase “water of hydration” refers to water which is somehowattractively bound to a non-water molecule. An exemplary form ofattraction includes hydrogen bonding. The water of hydration alsofunctions to increase the viscosity of the mixture during processing andcooling to prevent separation of the components. The amount of water ofhydration in the detergent composition will depend on the alkali metalhydroxide/hydratable salt. In addition to water of hydration, thedetergent composition may also have free water which isn't attractivelybound to a non-water molecule.

The detergent composition also includes a polysaccharide hybrid polymercomposition and PBTC. As discussed above, the polysaccharide hybridpolymer composition and PBTC combination may be particularly helpful incontrolling hard water scale. A suitable concentration of the of thepolysaccharide hybrid polymer composition and PBTC combination in thedetergent compositions is from about 0.5% to about 25% by weight of thedetergent composition. A particularly suitable concentration of thepolysaccharide hybrid polymer composition and PBTC combination in thedetergent compositions is from about 1% to about 15% by weight of thedetergent composition,

The polysaccharide hybrid polymer composition can be a bio-based and/orbiodegradable polymer, which reduces the reliance on natural gas and/orpetrochemical feedstocks. Biobased content is the amount of biobasedcarbon in a material or product and can be expressed as a percent ofweight (mass) of the total organic carbon in the product. The biobasedcontent can be determined using ASTM Method D6866, entitled StandardTest Methods for Determining the Biobased Content of Natural RangeMaterials Using Radiocarbon and Isotrope Ratio Mass SpectrometryAnalysis, Biodegradability measures the ability of microorganismspresent in the disposal environment to completely consume the biobasedcarbon product within a reasonable time frame and in a specifiedenvironment. In one example, the polysaccharide hybrid polymercomposition can include a polysaccharide and a reduced level ofpetrochemicals. For example, the detergent composition may include atleast about 10 wt % biodegradable content. In another example, thedetergent composition may include from about 10 wt % o about 80 wt %biodegradable content by weight.

The detergent compositions of the present invention can be provided inany of a variety of embodiments of detergent compositions. In anembodiment, the detergent composition is substantially free ofphosphorous, nitrilotriacetic acid (NTA) and ethylenediaminetetraaceticacid (EDTA). Phosphorus-free means a composition having less thanapproximately 0.5 wt %, more particularly, less than approximately 0.1wt %, and even more particularly less than approximately 0.01 wt %phosphorous based on the total weight of the composition. NTA-free meansa composition having less than approximately 0.5 wt %, less thanapproximately 0.1 wt %, and particularly less than approximately 0.01 wt% NTA based on the total weight of the composition. When the compositionis NTA-free, it is also compatible with chlorine, which functions as ananti-redeposition and stain-removal agent. When diluted to a usesolution, the detergent composition includes phosphorous-containingcomponents, NTA and EDTA concentrations of less than approximately 100ppm, particularly less than approximately 10 ppm, and more particularlyless than approximately 1 ppm.

Additional Functional Materials

The composition can also include various additional functionalcomponents. In some embodiments, the polysaccharide hybrid polymercomposition and PBTC make up a large amount, or even substantially allof the total weight of the detergent composition, for example, inembodiments having few or no additional functional materials disposedtherein. In one specific example, the composition consists essentiallyof the polysaccharide hybrid polymer composition and PBTC. In theseembodiments, the component concentration ranges provided above for thedetergent are representative of the ranges of those same components inthe detergent composition.

In other embodiments, the alkali metal hydroxide, water,2-phosphonabutane-1,2,4-tricarboxylic acid or salts thereof, and thepolysaccharide hybrid polymer composition make up a large amount, oreven substantially all of the total weight of the composition, forexample, in embodiments having few or no additional functional materialsdisposed therein. In one specific example, the composition consistsessentially of the alkali metal hydroxide, water,2-phosphonobutane-1,2,4-tricarboxylic acid or salts thereof, and thepolysaccharide hybrid polymer composition. In these embodiments, thecomponent concentration ranges provided above for the detergent arerepresentative of the ranges of those same components in thecomposition.

In alternative embodiments, functional materials are added to providedesired properties and functionalities to the composition. For thepurpose of this application, the term “functional materials” includes amaterial that when dispersed or dissolved in a use and/or concentratesolution, such as an aqueous solution, provides a beneficial property ina particular use. Some particular examples of functional materials arediscussed in more detail below, although the particular materialsdiscussed are given by way of example only, and that a broad variety ofother functional materials may be used. Moreover, the componentsdiscussed above may be multi-functional and may also provide several ofthe functional benefits discussed below.

Secondary Alkali Source

The composition can include one or more secondary alkali sources.Examples of suitable secondary alkali sources of the compositioninclude, but are not limited to alkali metal carbonates, alkali metalhydroxides and alkali metal silicates. Exemplary alkali metal carbonatesthat can be used include, but are not limited to: sodium or potassiumcarbonate, bicarbonate, sesquicarbonate, and mixtures thereof. Exemplaryalkali metal hydroxides that can be used include, but are not limitedto: sodium or potassium hydroxide. The alkali metal hydroxide may beadded to the composition in any form known in the art, including assolid beads, dissolved in an aqueous solution, or a combination thereof.Examples of alkali metal silicates include, but are not limited tosodium or potassium silicate or polysilicate, sodium or potassiummetasilicate and hydrated sodium or potassium metasilicate or acombination thereof.

Surfactants

The composition may also include a surfactant. A variety of surfactantscan be used in the composition, including, but not limited to: anionic,nonionic, cationic, and zwitterionic surfactants. Exemplary surfactantsthat can be used are commercially available from a number of sources.For a discussion of surfactants, see Kirk-Othmer, Encyclopedia ofChemical Technology, Third Edition, volume 8, pages 900-912. When thecomposition includes a surfactant as a cleaning agent, the cleaningagent is provided in an amount effective to provide a desired level ofcleaning. The composition, when provided as a concentrate, can includethe surfactant cleaning agent in a range of about 0.05% to about 20% byweight, about 0.5% to about 15% by weight, about 1% to about 15% byweight, about 1.5% to about 10% by weight, and about 2% to about 8% byweight. Additional exemplary ranges of surfactant in a concentrateinclude about 0.5% to about 8% by weight, and about 1% to about 5% byweight.

Examples of anionic surfactants useful in the composition include, butare not limited to: carboxylates such as alkylcarboxylates andpolyalkoxycarboxylates, alcohol ethoxylate carboxylates, nonylphenolethoxylate carboxylates; sulfonates such as alkylsulfonates,alkylbenzenesulfonates, alkylarylsulfonates, sulfonated fatty acidesters; sulfates such as sulfated alcohols, sulfated alcoholethoxylates, sulfated alkylphenols, alkylsulfates, sulfosuccinates, andalkylether sulfates. Exemplary anionic surfactants include, but are notlimited to: sodium alkylarylsulfonate, alpha-olefinsulfonate, and fattyalcohol sulfates.

Examples of nonionic surfactants useful in the composition include, butare not limited to, those having a polyalkylene oxide polymer as aportion of the surfactant molecule. Such nonionic surfactants include,but are not limited to: chlorine-, benzyl-, methyl-, ethyl-, (propyl-,butyl- and other like alkyl-capped polyethylene glycol ethers of fattyalcohols; polyalkylene oxide free nonionics such as alkylpolyglycosides; sorbitan and sucrose esters and their ethoxylates;alkoxylated amines such as alkoxylated ethylene diamine; alcoholalkoxylates such as alcohol ethoxylate propoxylates, alcoholpropoxylates, alcohol propoxylate ethoxylate propoxylates, alcoholethoxylate butoxylates; nonylphenol ethoxylate, polyoxyethylene glycolether; carboxylic acid esters such as glycerol esters, polyoxyethyleneesters, ethoxylated and glycol esters of fatty acids; carboxylic amidessuch as diethanolamine condensates, monoalkanolamine condensates,polyoxyethylene fatty acid amides; and polyalkylene oxide blockpolymers. An example of a commercially available ethyleneoxide/propylene oxide block polymer includes, but is not limited to,PLURONIC®, available from BASF Corporation, Florham Park, N.J. andBEROL® available from AkzoNobel Surface Chemistry, Chicago, Ill. Anexample of a commercially available silicone surfactant includes, but isnot limited to, ABIL® B8852, available from Goldschmidt ChemicalCorporation, Hopewell, Va. A particularly suitable surfactant is D500,an ethylene oxide/propylene oxide polymer available from BASFCorporation, Florham Park, N.J.

Examples of cationic surfactants that can be used in the compositioninclude, but are not limited to: amines such as primary, secondary andtertiary monoamines with C₁₈ alkyl or alkenyl chains, ethoxylatedalkylamines, alkoxylates of ethylenediamine, imidazoles such as a1-(2-hydroxyethyl)-2-imidazoline, a2-alkyl-1-(2-hydroxyethyl)-2-imidazoline, and the like; and quaternaryammonium salts, as for example, alkylquaternary ammonium chloridesurfactants such as n-alkyl(C₁₂-C₁₈)dimethylbenzyl ammonium chloride,n-tetradecyldimethylbenzylammonium chloride monohydrate, and anaphthylene-substituted quaternary ammonium chloride such asdimethyl-1-naphthylmethylammonium chloride. The cationic surfactant canbe used to provide sanitizing properties.

Examples of zwitterionic surfactants that can be used in the compositioninclude, but are not limited to: betaines, imidazolines, andpropionates.

When the composition is intended to be used in an automatic dishwashingor warewashing machine, the surfactants selected, if any surfactant isused, can be those that provide an acceptable level of foaming when usedinside a dishwashing or warewashing machine. Compositions for use inautomatic dishwashing or warewashing machines are generally consideredto be low-foaming compositions. Low foaming surfactants that provide thedesired level of detersive activity are advantageous in an environmentsuch as a dishwashing machine where the presence of large amounts offoaming can be problematic. In addition to selecting low foamingsurfactants, defoaming agents can also be utilized to reduce thegeneration of foam. Accordingly, surfactants that are considered lowfoaming surfactants can be used. In addition, other surfactants can beused in conjunction with a defoaming agent to control the level offoaming.

Builders or Water Conditioners

The composition can include one or more building agents, also calledchelating or sequestering agents (e.g., builders), including, but notlimited to: condensed phosphates, alkali metal carbonates, phosphonates,aminocarboxylic acids, and/or polyacrylates. In general, a chelatingagent is a molecule capable of coordinating (i.e., binding) the metalions commonly found in natural water to prevent the metal ions frominterfering with the action of the other detersive ingredients of acleaning composition. Preferable levels of addition for builders thatcan also be chelating or sequestering agents are from about 0.1% toabout 70% by weight, about 1% to about 60% by weight, or about 1.5% toabout 50% by weight, based on the total weight of the composition. Ifthe solid composition is provided as a concentrate, the concentrate caninclude from approximately 1% to approximately 60% by weight, fromapproximately 3% to approximately 50% by weight, and from approximately6% to approximately 45% by weight of the builders, based on the totalweight of the concentrate. Additional ranges of the builders includefrom approximately 3% to approximately 20% by weight, from approximately6% to approximately 15% by weight, from, approximately 25% toapproximately 50% by weight, and from approximately 35% to approximately45% by weight, based on the total weight of the composition.

Examples of condensed phosphates include, but are not limited to: sodiumand potassium orthophosphate, sodium and potassium pyrophosphate, sodiumtripolyphosphate, and sodium hexametaphosphate. A condensed phosphatemay also assist, to a limited extent, in solidification of thecomposition by fixing the free water present in the composition as waterof hydration.

Examples of phosphonates include, but are not limited to:2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC),1-hydroxyetharte-1,1-diphosphonic acid, CH₂C(OH)[PO(OH)₂]₂;aminotri(methylenephosphonic acid), N[CH₂ PO(OH)₂]₃;arninotri(methylenephosphonate), sodium salt (ATMP), N[CH₂ PO(ONa)₂]₃;2-hydroxyethyliminobis(methytenephosphonic acid), HOCH₂CH₂ N[CH₂PO(OH)₂]₂; diethylenetriaminepenta(methylenephosphonic acid), (HO)₂POCH₂N[CH₂ CH₂ N[CH₂ PO(OH)₂]₂]₂;diethylenetriaminepenta(methylenephosphonate), sodium salt (DTPMP), C₉H_((28-x)) N₃ Na_(x)O₁₅ P₅ (x=7);hexamethylenediamine(tetramethylenephosphonate), potassium salt,C₁₀H_((28-x)) N₂K_(X) O₁₂ P₄ (x=6);bis(hexamethylene)triamine(pentamethylenephosphonic acid), (HO₂)POCH₂N[(CH₂)₂N[CH₂ PO(OH)₂]₂]₂; and phosphorus acid, H₃PO₃. A preferredphosphonate combination is ATMP and DTPMP. A neutralized or alkaliphosphonate, or a combination of the phosphonate with an alkali sourceprior to being added into the mixture such that there is little or noheat or gas generated by a neutralization reaction when the phosphonateis added is preferred. In one embodiment, however, the composition isphosphorous-free.

Useful aminocarboxylic acid materials containing little or no NTAinclude, but are not limited to: N-hydroxyethylaminodiacetic acid,ethylenediaminetetraacetic acid (EDTA),hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaaceticacid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), methylglycinediacetic acid(MGDA), glutamic acid-N,N-diacetic acid (GLDA), ethylenediaminesuccinicacid (EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinicacid (IDS), 3-hydroxy-2-2′-iminodisuccinic acid (HIDS) and other similaracids or salts thereof having an amino group with a carboxylic acidsubstituent. In one embodiment, however, the composition is free ofaminocarboxylates.

Water conditioning polymers can be used as non-phosphorus containingbuilders. Exemplary water conditioning polymers include, but are notlimited to: polycarboxylates. Exemplary polycarboxylates that can beused as builders and/or water conditioning polymers include, but are notlimited to: those having pendant carboxylate (—CO₂ ⁻) groups such aspolyacrylic acid, maleic acid, maleic/olefin polymer, sulfonated polymeror terpolymer, acrylic/maleic polymer, polymethacrylic acid, acrylicacid-methacrylic acid polymers, hydrolyzed polyacrylamide, hydrolyzedpolymethacrylamide, hydrolyzed polyamide-methacrylamide polymers,hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, andhydrolyzed acrylonitrile-methacrylonitrile polymers. Other suitablewater conditioning polymers include starch, sugar or polyols comprisingcarboxylic acid or ester functional groups. Exemplary carboxylic acidsinclude but are not limited to maleic acid, acrylic, methacrylic anditaconic acid or salts thereof. Exemplary ester functional groupsinclude aryl, cyclic, aromatic and C₁-C₁₀ linear, branched orsubstituted esters. For a further discussion of chelatingagents/sequestrants, see Kirk-Othmer, Encyclopedia of ChemicalTechnology, Third Edition, volume 5, pages 339-366 and volume 23, pages319-320, the disclosure of which is incorporated by reference herein.These materials may also be used at substoichiometric levels to functionas crystal modifiers

Hardening Agents

The compositions can also include a hardening agent in addition to, orin the form of, the builder. A hardening agent is a compound or systemof compounds, organic or inorganic, which significantly contributes tothe uniform solidification of the composition. Preferably, the hardeningagents are compatible with the cleaning agent and other activeingredients of the composition and are capable of providing an effectiveamount of hardness and/or aqueous solubility to the processedcomposition. The hardening agents should also be capable of forming ahomogeneous matrix with the cleaning agent and other ingredients whenmixed and solidified to provide a uniform dissolution of the cleaningagent from the composition during use.

The amount of hardening agent included in the composition will varyaccording to factors including, but not limited to: the type ofcomposition being prepared, the ingredients of the composition, theintended use of the composition, the quantity of dispensing solutionapplied to the solid composition over time during use, the temperatureof the dispensing solution, the hardness of the dispensing solution, thephysical size of the composition, the concentration of the otheringredients, and the concentration of the cleaning agent in thecomposition. It is preferred that the amount of the hardening agentincluded in the composition is effective to combine with the cleaningagent and other ingredients of the composition to form a homogeneousmixture under continuous mixing conditions and a temperature at or belowthe melting temperature of the hardening agent.

It is also preferred that the hardening agent form a matrix with thecleaning agent and other ingredients which will harden to a solid formunder ambient temperatures of approximately 30° C. to approximately 50°C., particularly approximately 35° C. to approximately 45° C., aftermixing ceases and the mixture is dispensed from the mixing system,within approximately 1 minute to approximately 3 hours, particularlyapproximately 2 minutes to approximately 2 hours, and particularlyapproximately 5 minutes to approximately 1 hour. A minimal amount ofheat from an external source may be applied to the mixture to facilitateprocessing of the mixture. It is preferred that the amount of thehardening agent included in the composition is effective to provide adesired hardness and desired rate of controlled solubility of theprocessed composition when placed in an aqueous medium to achieve adesired rate of dispensing the cleaning agent from the solidifiedcomposition during use.

The hardening agent may be an organic or an inorganic hardening agent. Apreferred organic hardening agent is a polyethylene glycol (PEG)compound. The solidification rate of compositions comprising apolyethylene glycol hardening agent will vary, at least in part,according to the amount and the molecular weight of the polyethyleneglycol added to the composition. Examples of suitable polyethyleneglycols include, but are not limited to: solid polyethylene glycols ofthe general formula H(OCH₂CH₂)_(n)OH, where n is greater than 15,particularly approximately 30 to approximately 1700. Typically, thepolyethylene glycol is a solid in the form of a free-flowing powder orflakes, having a molecular weight of approximately 1,000 toapproximately 100,000, particularly having a molecular weight of atleast approximately 1,450 to approximately 20,000, more particularlyfrom approximately 1,450 to approximately 8,000. The polyethylene glycolis present at a concentration of from approximately 1% to 75% by weightand particularly approximately 3% to approximately 15% by weight, basedon the total weight of the composition. Suitable polyethylene glycolcompounds include, but are not limited to: PEG 4000, PEG 1450, and PEG8000 among others, with PEG 4000 and PEG 8000 being most preferred. Anexample of a commercially available solid polyethylene glycol includes,but is not limited to: CARBOWAX, available from Union CarbideCorporation, Houston, Tex.

Preferred inorganic hardening agents are hydratable inorganic salts,including, but not limited to: sulfates, carbonates and bicarbonates.The inorganic hardening agents are present at concentrations of up toapproximately 50% by weight, from approximately 5% to approximately 50%by weight, particularly approximately 5% to approximately 25% by weight,and more particularly approximately 5% to approximately 15% by weight,based on total weight of the composition. In one embodiment, however,the solid composition is free of sulfates and carbonates including sodaash.

Urea particles can also be employed as hardeners in the compositions.The solidification rate of the compositions will vary, at least in part,to factors including, but not limited to: the amount, the particle size,and the shape of the urea added to the composition. For example, aparticulate form of urea can be combined with a cleaning agent and otheringredients, and preferably a minor but effective amount of water. Theamount and particle size of the urea is effective to combine with thecleaning agent and other ingredients to form a homogeneous mixturewithout the application of heat from an external source to melt the ureaand other ingredients to a molten stage. It is preferred that the amountof urea included in the composition is effective to provide a desiredhardness and desired rate of solubility of the composition when placedin an aqueous medium to achieve a desired rate of dispensing thecleaning agent from the solidified composition during use. In someembodiments, the composition includes from approximately 5% toapproximately 90% by weight urea, particularly from approximately 8% toapproximately 40% by weight urea, and more particularly fromapproximately 10% to approximately 30% by weight urea, based on totalweight of the composition.

The urea may be in the form of prilled beads or powder. Prilled urea isgenerally available from commercial sources as a mixture of particlesizes ranging from about 8-15 U.S. mesh, as for example, from ArcadianSohio Company, Nitrogen Chemicals Division. A prilled form of urea ispreferably milled to reduce the particle size to about 50 U.S. mesh toabout 125 U.S. mesh, particularly about 75-100 U.S. mesh, preferablyusing a wet mill such as a single or twin-screw extruder, a Teledynemixer, a Ross emulsifier, and the like.

Bleaching Agents

Bleaching agents suitable for use in the composition for lightening orwhitening a substrate include bleaching compounds capable of liberatingan active halogen species, such as Cl₂, Br₂, —OCl⁻ and/or —OBr⁻, underconditions typically encountered during the cleansing process. Suitablebleaching agents for use in the compositions include, but are notlimited to: chlorine-containing compounds such as chlorine,hypochlorites, or chloramines. Exemplary halogen-releasing compoundsinclude, but are not limited to: the alkali metal dichloroisocyanurates,chlorinated trisodium phosphate, the alkali metal hypochlorites,monochloramine, and dichloramine. Encapsulated chlorine sources may alsobe used to enhance the stability of the chlorine source in thecomposition (see, for example, U.S. Pat. Nos. 4,618,914 and 4,830,773,the disclosure of which is incorporated by reference herein). Ableaching agent may also be a peroxygen or active oxygen source such ashydrogen peroxide, perborates, sodium carbonate peroxyhydrate, potassiumpermonosulfate, and sodium perborate mono and tetrahydrate, with andwithout activators such as tetraacetylethylene diamine. When theconcentrate includes a bleaching agent, it can be included in an amountfrom approximately 0.1% to approximately 60% by weight, fromapproximately 1% to approximately 20% by weight, from approximately 3%to approximately 8% by weight, and from approximately 3% toapproximately 6% by weight, based on the total weight of thecomposition.

Fillers

The composition can include an effective amount of detergent fillerswhich do not perform as a cleaning agent per se, but cooperates with thecleaning agent to enhance the overall cleaning capacity of thecomposition. Examples of detergent fillers suitable for use in thepresent cleaning compositions include, but are not limited to: sodiumsulfate and sodium chloride. When the concentrate includes a detergentfiller, it can be included in an amount up to approximately 50% byweight, from approximately 1% to approximately 30% by weight, or fromapproximately 1.5% from approximately 25% by weight, based on totalweight of the composition.

Defoaming Agents

A defoaming agent for reducing the stability of foam may also beincluded in the composition. Examples of defoaming agents include, butare not limited to: ethylene oxide/propylene block polymers such asthose available under the name Pluronic® N-3 available from BASFCorporation, Florham Park, N.J.; silicone compounds such as silicadispersed in polydimethylsiloxane, polydimethylsiloxane, andfunctionalized polydimethylsiloxane such as those available under thename Abil® B9952 available from Goldschmidt Chemical Corporation,Hopewell, Va.; fatty amides, hydrocarbon waxes, fatty acids, fattyesters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils,polyethylene glycol esters, and alkyl phosphate esters such asmonostearyl phosphate. A discussion of defoaming agents may be found,for example, in U.S. Pat. No. 3,048,548 to Martin et al, U.S. Pat. No.3,334,147 to Brunelle et al., and U.S. Pat. No. 3,442,242 to Rue et al.,the disclosures of which are incorporated herein by reference. When theconcentrate includes a defoaming agent, the defoaming agent can beprovided in an amount from approximately 0.0001% to approximately 10% byweight, from approximately 0.001% to approximately 5% by weight, or fromapproximately 0.01% toapproximately 1.0% by weight, based on totalweight of the composition.

Anti-Redeposition Agents

The composition can include an anti-redeposition agent for facilitatingsustained suspension of soils in a cleaning solution and preventing theremoved soils from being redeposited onto the substrate being cleaned.Examples of suitable anti-redeposition agents include, but are notlimited to: polyacrylates, styrene maleic anhydride polymers, cellulosicderivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose andcarboxymethyl cellulose. When the concentrate includes ananti-redeposition agent, the anti-redeposition agent can be included inan amount from approximately 0.5% to approximately 10% by weight, andfrom approximately 1% to approximately 5% by weight, based on totalweight of the composition.

Stabilizing Agents

The composition may also include stabilizing agents. Examples ofsuitable stabilizing agents include, but are not limited to: borate,calcium/magnesium ions, propylene glycol, and mixtures thereof. Theconcentrate need not include a stabilizing agent, but when theconcentrate includes a stabilizing agent, it can be included in anamount that provides the desired level of stability of the concentrate.Exemplary ranges of the stabilizing agent include up to approximately20% by weight, from approximately 0.5% to approximately 20% by weight,from approximately 0.5% to approximately 15% by weight, and fromapproximately 2% to approximately 10% by weight, based on total weightof the composition.

Dispersants

The composition may also include dispersants. Examples of suitabledispersants that can be used in the composition include, but are notlimited to: maleic acid/olefin polymers, polyacrylic acid, and mixturesthereof. The concentrate need not include a dispersant, but when adispersant is included it can be included in an amount that provides thedesired dispersant properties. Exemplary ranges of the dispersant in theconcentrate can be up to approximately 20% by weight, from approximately0.5% to approximately 20% by weight, from approximately 0.5% toapproximately 15% by weight, and from approximately 2% to approximately9% by weight based on the total weight of the composition.

Enzymes

Enzymes that can be included in the composition include those enzymesthat aid in the removal of starch and/or protein stains. Exemplary typesof enzymes include, but are not limited to: proteases, alpha-amylases,and mixtures thereof. Exemplary proteases that can be used include, butare not limited to: those derived from Bacillus licheniformix, Bacilluslenus, Bacillus alcalophilus, and Bacillus amyloliquefacins. Exemplaryalpha-amylases include Bacillus subtilis, Bacillus amyloliquefaceins andBacillus licheniformis. The concentrate need not include an enzyme, butwhen the concentrate includes an enzyme, it can be included in an amountthat provides the desired enzymatic activity when the composition isprovided as a use composition. Exemplary ranges of the enzyme in theconcentrate include up to approximately 15% by weight, fromapproximately 0.5% to approximately 15% by weight, from approximately0.5% to approximately 10% by weight, and from approximately 1% toapproximately 5% by weight, based on total weight of the composition.

Fragrances and Dyes

Various dyes, odorants including perfumes, and other aesthetic enhancingagents can also be included in the composition. Suitable dyes that maybe included to alter the appearance of the composition, include, but arenot limited to: Direct Blue 86, available from Mac Dye-Chem Industries,Ahmedabad, India; Fastusol Blue, available from Mobay ChemicalCorporation, Pittsburgh, Pa.; Acid Orange 7, available from AmericanCyanamid Company, Wayne, N.J.; Basic Violet 10 and Sandolan Blue/AcidBlue 182, available from Sandoz, Princeton, N.J.; Acid Yellow 23,available from Chemos GmbH, Regenstauf, Germany; Acid Yellow 17,available from Sigma Chemical, St. Louis, Mo.; Sap Green and MetanilYellow, available from Keyston Analine and Chemical, Chicago, Ill.; AcidBlue 9, available from Emerald Hilton Davis, LLC, Cincinnati, Ohio;Hisol Fast Red and Fluorescein, available from Capitol Color andChemical Company, Newark, N.J.; and Acid Green 25, Ciba SpecialtyChemicals Corporation, Greenboro, N.C.

Fragrances or perfumes that may be included in the compositions include,but are not limited to: terpenoids such as citronellol, aldehydes suchas amyl cinnamaldehyde, a jasmine such as C1S-jasmine or jasmal, andvanillin.

In an embodiment, these aesthetic enhancing agents can be included inthe composition in an amount from about 0.1% to about 5%, based on totalweight of the composition.

Thickeners

The compositions can include a rheology modifier or a thickener. Therheology modifier may provide the following functions: increasing theviscosity of the compositions; increasing the particle size of liquiduse compositions when dispensed through a spray nozzle; providing theuse compositions with vertical cling to surfaces; providing particlesuspension within the use compositions; or reducing the evaporation rateof the use compositions.

The rheology modifier may provide a use composition that is pseudoplastic, in other words the use composition or material when leftundisturbed (in a shear mode), retains a high viscosity. However, whensheared, the viscosity of the material is substantially but reversiblyreduced. After the shear action is removed, the viscosity returns. Theseproperties permit the application of the material through a spray head.When sprayed through a nozzle, the material undergoes shear as it isdrawn up a feed tube into a spray head under the influence of pressureand is sheared by the action of a pump in a pump action sprayer. Ineither case, the viscosity can drop to a point such that substantialquantities of the material can be applied using the spray devices usedto apply the material to a soiled surface. However, once the materialcomes to rest on a soiled surface, the materials can regain highviscosity to ensure that the material remains in place on the soil.Preferably, the material can be applied to a surface resulting in asubstantial coating of the material that provides the cleaningcomponents in sufficient concentration to result in lifting and removalof the hardened or baked-on soil. While in contact with the soil onvertical or inclined surfaces, the thickeners in conjunction with theother components of the cleaner minimize dripping, sagging, slumping orother movement of the material under the effects of gravity. Thematerial should be formulated such that the viscosity of the material isadequate to maintain contact between substantial quantities of the filmof the material with the soil for at least a minute, particularly fiveminutes or more.

Examples of suitable thickeners or rheology modifiers are polymericthickeners including, but not limited to: polymers or natural polymersor gums derived from plant or animal sources. Such materials may bepolysaccharides such as large polysaccharide molecules havingsubstantial thickening capacity. Thickeners or rheology modifiers alsoinclude clays.

A substantially soluble polymeric thickener can be used to provideincreased viscosity or increased conductivity to the use compositions.Examples of polymeric thickeners for the aqueous compositions of theinvention include, but are not limited to: carboxylated vinyl polymerssuch as polyacrylic acids and sodium salts thereof, ethoxylatedcellulose, polyacrylamide thickeners, cross-linked, xanthancompositions, sodium alginate and algin products, hydroxypropylcellulose, hydroxyethyl cellulose, and other similar aqueous thickenersthat have some substantial proportion of water solubility. Examples ofsuitable commercially available thickeners include, but are not limitedto: Acusol, available from Rohm & Haas Company, Philadelphia, Pa.;ALCOGUM® available from AkzoNobel, Chicago, Ill. and Carbopol, availablefrom B.F. Goodrich, Charlotte, N.C.

Examples of suitable polymeric thickeners include, but not limited to:polysaccharides. An example of a suitable commercially availablepolysaccharide includes, but is not limited to, Diutan, available fromKelco Division of Merck, San Diego, Calif. Thickeners for use in thecompositions further include polyvinyl alcohol thickeners, such as,fully hydrolyzed (greater than 98.5 mol acetate replaced with the —OHfunction).

An example of a particularly suitable polysaccharide includes, but isnot limited to, xanthans. Such xanthan polymers are preferred due totheir high water solubility, and great thickening power. Xanthan is anextracellular polysaccharide of xanthomonas campestras. Xanthan may bemade by fermentation based on corn sugar or other corn sweetenerby-products. Xanthan comprises a poly beta-(1-4)-D-Glucopyranosylbackbone chain, similar to that found in cellulose. Aqueous dispersionsof xanthan gum and its derivatives exhibit novel and remarkablerheological properties. Low concentrations of the gum have relativelyhigh viscosities which permit it to be used economically. Xanthan gumsolutions exhibit high pseudo plasticity, i.e. over a wide range ofconcentrations, rapid shear thinning occurs that is generally understoodto be instantaneously reversible. Non-sheared materials have viscositiesthat appear to be independent of the pH and independent of temperatureover wide ranges. Preferred xanthan materials include crosslinkedxanthan materials. Xanthan polymers can be crosslinked with a variety ofknown covalent reacting crosslinking agents reactive with the hydroxylfunctionality of large polysaccharide molecules and can also becrosslinked using divalent, trivalent or polyvalent metal ions. Suchcrosslinked xanthan gels are disclosed in U.S. Pat. No. 4,782,901, whichis herein incorporated by reference. Suitable crosslinking agents forxanthan materials include, but are not limited to: metal cations such asA1+3, Fe+3, Sb+3, Zr+4 and other transition metals. Examples of suitablecommercially available xanthans include, but are not limited to:KELTROL®, KELZAN® AR, KELZAN® D35, KELZAN® S, KELZAN® XZ, available fromKelso Division of Merck, San Diego, Calif. Known organic crosslinkingagents can also be used. A preferred crosslinked xanthan is KELZAN® AR,which provides a pseudo plastic use composition that can produce largeparticle size mist or aerosol when sprayed.

In an embodiment, the rheology modifiers and thickeners may be includedin the composition in an amount from about 0.1 to about 5.0 weight %,based on total weight of the composition.

Methods of Manufacture

In general, the composition of the present invention can be created bycombining the 2-phosphonobutane-1,2,4-tricarboxylic acid, thepolysaccharide hybrid polymer composition and any additional functionalcomponents and allowing the components to interact.

In one example, the alkali metal hydroxide, water,2-phosphonobutane-1,2,4-tricarboxylic acid, the polysaccharide hybridpolymer composition and any additional functional components interactand harden into solid form. The solidification process may last from afew minutes to about six hours, depending on factors including, but notlimited to: the size of the formed or cast composition, the ingredientsof the composition, and the temperature of the composition.

The solid compositions may be formed using a batch or continuous mixingsystem. In an exemplary embodiment, a single- or twin-screw extruder isused to combine and mix one or more cleaning agents at high shear toform a homogeneous mixture. In some embodiments, the processingtemperature is at or below the melting temperature of the components.The processed mixture may be dispensed from the mixer by forming,casting or other suitable means, whereupon the composition hardens to asolid form. The structure of the matrix may be characterized accordingto its hardness, melting point, material distribution, crystalstructure, and other like properties according to known methods in theart. Generally, a solid composition processed according to the method ofthe invention is substantially homogeneous with regard to thedistribution of ingredients throughout its mass and is dimensionallystable.

In an extrusion process, the liquid and solid components are introducedinto final mixing system and are continuously mixed until the componentsform a substantially homogeneous semi-solid mixture in which thecomponents are distributed throughout its mass. The mixture is thendischarged from the mixing system into, or through, a die or othershaping means. The product is then packaged. In an exemplary embodiment,the formed composition begins to harden to a solid form in fromapproximately 1 minute to approximately 3 hours. Particularly, theformed composition begins to harden to a solid form from approximately 1minute to approximately 2 hours. More particularly, the formedcomposition begins to harden to a solid form from approximately 1 minuteto approximately 20 minutes.

In a casting process, the liquid and solid components are introducedinto the final mixing system and are continuously mixed until thecomponents form a substantially homogeneous liquid mixture in which thecomponents are distributed throughout its mass. In an exemplaryembodiment, the components are mixed in the mixing system for at leastapproximately 60 seconds. Once the mixing is complete, the product istransferred to a packaging container where solidification takes place.In an exemplary embodiment, the cast composition begins to harden to asolid form in from approximately 1 minute to approximately 3 hours.Particularly, the cast composition begins to harden to a solid form infrom approximately 1 minute to approximately 2 hours. More particularly,the cast composition begins to harden to a solid form approximately 1minute to approximately 20 minutes.

By the term “solid”, it is meant that the hardened composition will notflow and will substantially retain its shape under moderate stress orpressure or mere gravity. The degree of hardness of the solid castcomposition may range from that of a fused solid product which isrelatively dense and hard, for example, like concrete, to a consistencycharacterized as being a hardened paste. In addition, the term “solid”refers to the state of the composition under the expected conditions ofstorage and use of the solid composition. In general, it is expectedthat the composition will remain in solid form when exposed totemperatures of up to approximately 100° F. and particularly up toapproximately 120° F.

The resulting solid composition may take forms including, but notlimited to: a cast solid product; an extruded, molded or formed solidpellet, block, tablet, powder, granule, flake; or the formed solid canthereafter be ground or formed into a powder, granule, or flake. In anexemplary embodiment, extruded pellet materials formed by thesolidification matrix have a weight of approximately 50 grams toapproximately 250 grams, extruded solids formed by the composition havea weight of approximately 100 grams or greater, and solid blockdetergents formed by the composition have a mass of approximately 1 toapproximately 10 kilograms. The solid compositions provide for astabilized source of functional materials. In some embodiments, thesolid composition may be dissolved, for example, in an aqueous or othermedium, to create a concentrated and/or use composition. The solutionmay be directed to a storage reservoir for later use and/or dilution, ormay be applied directly to a point of use.

In certain embodiments, the solid composition is provided in the form ofa unit dose. A unit dose refers to a solid composition unit sized sothat the entire unit is used during a single washing cycle. When thesolid composition is provided as a unit dose, it is typically providedas a cast solid, an extruded pellet, or a tablet having a size ofapproximately 1 gram to approximately 50 grams.

In other embodiments, the solid composition is provided in the form of amultiple-use solid, such as a block or a plurality of pellets, and canbe repeatedly used to generate aqueous compositions for multiple washingcycles. In certain embodiments, the solid composition is provided as acast solid, an extruded block, or a tablet having a mass ofapproximately 5 grams to approximately 10 kilograms. In certainembodiments, a multiple-use form of the solid composition has a mass ofapproximately 1 kilogram to approximately 10 kilograms. In furtherembodiments, a multiple-use form of the solid composition has a mass ofof approximately 5 kilograms to approximately 8 kilograms. In otherembodiments, a multiple-use form of the solid composition has a mass ofabout approximately 5 grams to approximately 1 kilogram, or ofapproximately 5 grams to approximately 500 grams.

Although the composition is discussed as being formed into a solidproduct, the composition may also be provided in the form of a paste orliquid. When the concentrate is provided in the form of a paste, enoughwater is added to the composition such that complete solidification ofthe composition is precluded. In addition, dispersants and othercomponents may be incorporated into the composition in order to maintaina desired distribution of components.

Methods of Use

The compositions can include concentrate compositions which may be addedto an aqueous system or may be diluted to form use compositions. Ingeneral, a concentrate refers to a composition that is intended to beadded to or diluted with water, and the composition that contactsarticles to be washed can be referred to as the use composition.

A use composition may be prepared from the concentrate by diluting theconcentrate with water at a dilution ratio that provides a usecomposition having desired detersive properties. The water that is usedto dilute the concentrate to form the use composition can be referred toas water of dilution or a dilutent, and can vary from one location toanother. The use composition can also include additional functionalingredients at a level suitable for cleaning, rinsing, or the like.

The concentrate compositions may essentially include only thepolysaccharide polymer and PBTC, and additional components and/orfunctional materials may be added as separate ingredients prior to thepoint of use or at the point of use. Alternatively, the concentratecompositions may include the polysaccharide polymer and PBTC as well asadditional components such as, but not limited to, at least one alkalimetal hydroxide.

The typical dilution factor is from approximately 1 to approximately10,000 but will depend on factors including water hardness, the amountof soil to be removed and the like. In one embodiment, the concentrateis diluted at a ratio of about 1:10 to about 1:1000 concentrate towater. Particularly, the concentrate is diluted at a ratio of about1:100 to about 1:5000 concentrate to water. More particularly, theconcentrate is diluted at a ratio of about 1:250 to about 1:2000concentrate to water.

A suitable concentration range of the components includes of about 1 toabout 500 parts-per-million (ppm) of the polysaccharide hybrid polymercomposition and of about 0.1 to about 200 ppm of PBTC. A particularlysuitable concentration range of the components includes from about 5 toabout 500 parts-per-million (ppm) of the polysaccharide hybrid polymercomposition and from about 0.5 to about 200 ppm of PBTC. Anotherparticularly suitable concentration range of the components includesfrom about 10 to about 100 ppm of the polysaccharide hybrid polymercomposition and from about 1 and about 150 ppm PBTC.

When an alkali metal hydroxide is present, a suitable concentrationrange of the components in the use composition includes about 1 to about1000 ppm alkali metal hydroxide, from about 0.1 to about 200 ppm PBTC,and from about 1 to about 500 ppm of the polysaccharide hybrid polymercomposition. A particularly suitable concentration range of thecomponents in the use composition includes from about 50 and about 1000ppm alkali metal hydroxide, from about 0.5 to about 200 ppm PBTC, andfrom about 5 to 500 ppm of the polysaccharide hybrid polymercomposition. Another particularly suitable concentration range of thecomponents in the use composition includes from about 200 to about 800ppm alkali metal hydroxide, from about 1 to about 150 ppm of PBTC, andfrom about 10 to about 100 ppm of the polysaccharide hybrid polymercomposition.

The composition can contain an effective concentration of the alkalimetal hydroxide so that use composition has a pH of at least about 9. Inone embodiment, the composition is a use composition that can be broughtinto contact to clean articles or substrates, such as glass, plastic,ceramic, and metal, and the polysaccharide hybrid polymer compositionand PBTC may function to prevent or remove re-deposition of protein onthe substrate.

EXAMPLES

The present invention is more particularly described in the followingexamples that are intended as illustrations only, since numerousmodifications and variations within the scope of the present inventionwill be apparent to those of skill in the art. Unless otherwise noted,all parts, percentages, and ratios reported in the following examplesare on a weight bases, and all reagents used in the examples wereobtained, or are available, from the chemical suppliers described below,or may be synthesized by conventional techniques.

Materials Used

Lime-A-Way: a hard water stain remover that eliminates lime, calcium andrust stains and is available from Reckitt Benckiser Ecolab, Inc., St.Paul, Minn.

Guardian Plus®: a warewashing detergent available from Ecolab, Inc., St.Paul, Minn.

Pluronic® N-3: a ethylene oxide/propylene oxide block polymer surfactantavailable from BASF Corporation.

Bayhibit® S: 2-phosphobutane-1,2,4-tricarboxylic acid tetrasodium saltavailable from Lanxess, Pittsburgh, Pa.

EXP 1: a polysaccharide hybrid polymer composition containing about 50%by weight polysaccharide residue and about 50% by weight acrylic acidresidue.

Solid Power XL®: a solid detergent containing sodium hydroxide availablefrom Ecolab, St. Paul, Minn.

Synthesis of EXP 1

A 2 liter reactor containing 538 grams of water and 280 grams of DE 10maltodextrin was heated to 95° C. A monomer solution consisting of 280grams of acrylic acid and 107 grams of water was added to the reactorover 2.5 hours. An initiator solution comprising of 37.3 grams of sodiumpersulfate in 118 grams of water was simultaneously added to the reactorover a period of 2.5 hours. The reaction product was held at 95° C. foran additional period of 1 hour. The polymer solution was partiallyneutralized by using 140.4 grams of 50% sodium hydroxide and then 0.2grams of Proxel GXL was added as a biocide. The resulting polysaccharidehybrid polymer composition contained about 50% by weight polysaccharideresidue and about 50% by weight acrylic acid residue.

Cleaning Libby Glasses

Six 10 oz. Libby glasses were prepared for laboratory warewashingprocedures by removing all film and foreign material from the glasssurface. A three-gallon stainless steel pail was filled with distilledwater and placed on a hot plate set on high. The pail was covered withaluminum foil and brought to boil.

While the water in the pail was brought to a boil, the Libby glasseswere placed on a glass rack and loaded in a Hobart AM-15 warewashmachine. The warewash machine had a washbath volume of 60 L, a rinsevolume of 4.5 L, a wash time of 50 seconds and a rinse time of 9seconds. The warewash machine was filled with hot soft water (130° F.minimum) and 20 grams of Lime-A-Way, the door was closed and theautomatic cycle was run.

When the cycle was complete, the warewash machine was drained, refilledwith hot soft water and 20 grams of Guardian Plus, and the automaticcycle was run. When the cycle was complete, the warewash machine wasdrained, refilled with hot soft water and 10 grams of sodiumtripolyphosphate, and the automatic cycle was run again.

After completion of the automatic cycle with polyphosphate, the machinewas drained and refilled with the boiling distilled water from the pail.The control panel was switched to a delime setting and the machine wasallowed to run with the distilled water for three minutes. After threeminutes, the glasses were removed and the tops of the glasses weremopped with a clean, dry towel. The glasses were allowed to dry in theglass rack. The rack may be elevated on one side to facilitate drainingand drying.

100 Cycle Warewashing Test

To determine the ability of various detergent compositions to removespots and film from ware, six Libby 10 oz. glass tumblers were preparedby removing all film and foreign material from the surfaces of theglasses as described above. A Hobart AM-15 warewash machine was thenfilled with an appropriate amount of water and the water was tested forhardness. After recording the hardness value, the tank heaters wereturned on. On the day of the experiments, the water hardness was 17grains (1 grain=17 parts-per-million). The warewash machine was turnedon and wash/rinse cycles were run through the machine until a washtemperature of between about 150° F. and about 160° F. and a rinsetemperature of between about 175° F. and about 190° F. were reached. Thecontroller was then set to dispense an appropriate amount of detergentinto the wash tank. The detergent was dispensed such that when thedetergent was mixed with water during the cycle to form a use solution,the detergent concentration in the use solution is specified in Table 1.The solution in the wash tank was titrated to verify detergentconcentration. The warewash machine had a washbath volume of 53 liters,a rinse volume of 2.8 liters, a washtime of 50 seconds, and a rinse timeof 9 seconds.

The six clean glass tumblers were placed diagonally in a Rabum rack andone Newport 10 oz. plastic tumbler was placed off-diagonally in theRabum rack (see FIG. 1 for arrangement) and the rack was placed insidethe warewash machine. (P=plastic tumbler; G=glass tumbler).

The 100 cycle test was then started. At the beginning of each washcycle, the appropriate amount of detergent was automatically dispensedinto the warewash machine to maintain the initial detergentconcentration. The detergent concentration was controlled byconductivity.

Upon completion of 100 cycles, the rack was removed from the warewashmachine and the glass and plastic tumblers were allowed to dry. Theglass and plastic tumblers were then graded for spot and filmaccumulation using an analytical light box evaluation. The light boxtest used a digital camera, a light box, a light source, a light meterand a control computer employing “Spot Advance” and “Image Pro Plus”commercial software. A glass to be evaluated was placed on its side onthe light box, and the intensity of the light source was adjusted to apredetermined value using the light meter. A photographic image of theglass was taken and saved to the computer. The software was then used toanalyze the upper half of the glass, and the computer displayed ahistogram graph with the area under the graph being proportional to thethickness of the film.

Generally, a lower light box score indicates that more light was able topass through the tumbler. Thus, the lower the light box score, the moreeffective the composition was at preventing scale on the surface of thetumbler.

Samples 1-4 and Comparative Samples A and B

Samples 1-4 included varying concentrations of Bayhihit S (phosphonate)and EXP 1 (polysaccharide hybrid polymer composition). The active waterconditioner package (active we package) was the same for each Sample.Comparison Sample A was a Solid Power XL available from Ecolab Inc., St,Paul. Comparison Sample B was similar to the Samples 1-4 but did notinclude Bayhibit or EXP 1. The component concentrations of the detergentcompositions of Samples 1-4 and Comparative Example B are presentedbelow in Table 1.

TABLE 1 Comp. SMP 1 SMP 2 SMP 3 SMP 4 SMP B Sodium hydroxide 67.09 67.0967.09 67.09 79.1 Water 16.07 23.92 18.73 21.33 18.9 Pluronic N3 1.711.71 1.71 1.71 2 EXP 1, 40.9% 15.13 0 10 5 0 Bayhibit S, 85% 0 7.28 2.474.87 0 Total 100 100 100 100 100 Active wc package 6.19 6.19 6.19 6.18 0Use concentration 750 750 750 750 636 (ppm)

Table 2 presents the total light box score for the glass tumblers,plastic tumblers, and all tumblers (SUM(glass), SUM(plastic),SUM(total), respectively). The average glass tumbler light box score isalso provided (Average(glass)).

TABLE 2 Average SUM(glass) SUM(plastic) SUM(total) (glass) SMP 1 34813528111 376246 58023 SMP 2 202015 22680 224695 33669 SMP 3 152432 18756171188 25405 SMP 4 154080 21004 175084 25680 Comp SMP A 147284 30191177475 24547 Comp SMP B 393210 65535 458745 65535

The polysaccharide hybrid polymer composition and PBTC combinationimproved the light box scores compared to Comparative Samples B whichdid not include the polysaccharide hybrid polymer composition and PBTC.A percentage difference is calculated by dividing the difference of twovalues by the average of two values. The percentage differences of thetotal light box score after 100 cycles using a polysaccharide hybridpolymer composition and PBTC compared to Comparative Sample B (which didnot include a polysaccharide hybrid polymer composition and PBTC) were91% for Sample 3, 90% for Sample 4, 103% for Sample 5, and 107% forSample 7.

The polysaccharide hybrid polymer composition and PBTC combination alsoshowed improvements over the use of the polysaccharide hybrid polymercomposition alone. For polysaccharide hybrid polymer composition EXP 1,the percentage difference of the total light box score after 100 cyclesof Sample 3 compared to Sample 1 was 68% and the difference betweenSample 4 and Sample 1 was 75%.

Further, as shown in Table 2, Samples 3 and 4, which included Bayhibit Sand polysaccharide hybrid polymer composition, were as effective as ormore effective than the solid detergent containing sodium hydroxide ofComparative Sample A in removing and/or preventing hard water scale.

Various modifications and additions can be made to the exemplaryembodiments discussed without departing from the scope of the presentinvention. For example, while the embodiments described above refer toparticular features, the scope of this invention also includesembodiments having different combinations of features and embodimentsthat do not include all of the above described features.

1. A cleaning composition comprising: at least one alkali metalhydroxide; water; 2-phosphonobutane-1,2,4-tricarboxylic acid or saltsthereof; and a polysaccharide hybrid polymer composition comprising:polysaccharide residue in an amount from approximately 5% toapproximately 90% by weight of the polysaccharide hybrid polymer; andresidue of at least one ethylenically unsaturated monomer present in anamount from approximately 10% to approximately 75% by weight of thepolysaccharide hybrid polymer composition.
 2. The cleaning compositionof claim 1 wherein the at least one ethylenically unsaturated monomerincludes at least one anionic ethylenically unsaturated monomer.
 3. Thecleaning composition of claim 1, wherein the at least one ethylenicallyunsaturated monomer includes at least one member selected from the groupconsisting of acrylic acid, methacrylic acid, ethacrylic acid,α-chloro-acrylic acid, α-cyano acrylic acid, β-methyl-acrylic acid(crotonic acid), α-phenyl acrylic acid, β-acryloxy propionic acid,sorbic acid, α-chloro sorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, β-styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3),itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconicacid, aconitic acid, fumaric acid, tricarboxy ethylene,2-acryloxypropionic acid, and salts and combinations thereof.
 4. Thecleaning composition of claim 3, wherein the at least one ethylenicallyunsaturated monomer includes at least one member selected from the groupconsisting of acrylic acid, maleic acid, methacrylic acid,2-acrylamido-2-methyl propane sulfonic acid, monomethyl maleate, andsalts and combinations thereof.
 5. The cleaning composition of claim 1,wherein the at least one alkali metal hydroxide includes sodiumhydroxide, potassium hydroxide, lithium hydroxide or combinationsthereof.
 6. The cleaning composition of claim 1, wherein thepolysaccharide hybrid polymer composition has a weight average molecularweight from approximately 2,000 g/mol to approximately 25,000 g/mol. 7.The cleaning composition of claim 1, wherein the polysaccharide hybridpolymer composition is present in an amount from about 0.1% to about 15%by weight of the cleaning composition.
 8. The cleaning composition ofclaim 7, wherein 2-phosphonobutane-1,2,4-tricarboxylic acid or saltsthereof are present in an amount from about 0.01% to about 10% by weightof the cleaning composition.
 9. The cleaning composition of claim 8,wherein the alkali metal hydroxide is present in an amount from about 1%to about 80% by weight of the cleaning composition.
 10. The cleaningcomposition of claim 1, wherein the2-phosphonobutane-1,2,4-tricarboxylic acid or salts thereof and thepolysaccharide hybrid polymer composition are present in a combinedamount from approximately 0.5% to approximately 25% by weight of thecleaning composition.
 11. The cleaning composition of claim 1, whereinthe cleaning composition contains about 10% or more biodegradablecontent by weight.
 12. A method of preparing a use solution, the methodcomprising: mixing water with a detergent composition to form the usesolution, wherein the use solution comprises: at least one alkali metalhydroxide present in an amount from about 1 ppm to about 1000 ppm;2-phosphonobutane-1,2,4-tricarboxylic acid or salts thereof present inan amount from about 0,1 ppm to about 200 ppm; and a polysaccharidehybrid polymer composition present in an amount from about 1 ppm toabout 500 ppm, wherein the polysaccharide hybrid polymer compositioncomprises from about 5% to about 90% by weight polysaccharide residueand from about 10% to about 75% by weight residue of at least oneethylenically unsaturated monomer.
 13. The method of claim 12, whereinthe at least one ethylenically unsaturated monomer includes at least oneanionic unsaturated monomer.
 14. The method of claim 12, wherein theleast one ethylenically unsaturated monomer includes at least one memberselected from the group consisting of acrylic acid, methacrylic acid,ethacrylic acid, α-chloro-acrylic acid, α-cyano acrylic acid,β-methyl-acrylic acid (crotonic acid), α-phenyl acrylic acid, β-acryloxypropionic acid, sorbic acid, α-chloro sorbic acid, angelic acid,cinnamic acid, p-chloro cinnamic acid, β-styryl acrylic acid(1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid,citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaricacid, tricarboxy ethylene, 2-acryloxypropionic acid,2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodiummethallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acidand monomethyl maleate, and salts and combinations thereof.
 15. Themethod of claim 14, wherein the at least one ethylenically unsaturatedmonomer includes at least one member selected from the group consistingof acrylic acid, maleic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, monomethyl maleate, and salts and combinationsthereof.
 16. The method of claim 12, wherein the at least one alkalimetal hydroxide includes sodium hydroxide, potassium hydroxide, lithiumhydroxide or combinations thereof.
 17. The method of claim 12, where thepolymer composition has a weight average molecular weight from about2,000 g/mol to about 25,000 g/mol.
 18. A method for controlling hardwater scale, the method comprising: adding an anionic polysaccharidehybrid polymer composition and 2-phosphonobutane-1,2,4-tricarboxylicacid or salts thereof to an aqueous system to control hard waterscaling, wherein the polysaccharide hybrid polymer compositioncomprises: residue of a polysaccharide present in an amount from about5% to about 90% the polysaccharide hybrid polymer composition; andresidue of at least one ethylenically unsaturated monomer present inamount from about 10% to about 75% weight of the polysaccharide hybridpolymer composition; and wherein the polysaccharide hybrid polymercomposition and 2-phosphonobutane-1,2,4-tricarboxylic acid or saltsthereof are added in amounts such that the aqueous system includes about1 to about 500 ppm polysaccharide hybrid polymer composition and fromabout 0.1 to about 200 ppm 2-phosphonobutane-1,2,4-tricarboxylic acid orsalts thereof.
 19. The method of claim 18, and further comprising:adding at least one alkali metal hydroxide to the aqueous system to forma use solution.
 20. The method of claim 18, wherein the polysaccharidehybrid polymer composition and the 2-phosphonobutane-1,2,4-tricarboxylicacid or salts thereof are present in a weight ratio from about 15:1 toabout 1:15.
 21. The method of claim 18, wherein the at least oneethylenically unsaturated monomer is anionic.
 22. The method of claim18, wherein the at least one ethylenically unsaturated monomer includesat least one member selected from the group consisting of acrylic acid,methacrylic acid, ethacrylic acid, α-chloro-acrylic acid, α-cyanoacrylic acid, β-methyl-acrylic acid (crotonic acid), α-phenyl acrylicacid, β-acryloxy propionic acid, sorbic acid, α-chloro sorbic acid,angelic acid, cinnamic acid, p-chloro cinnamic acid, β-styryl acrylicacid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid,citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaricacid, tricarboxy ethylene, 2-acryloxypropionic acid,2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodiummethallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acidand monomethyl maleate, and salts and combinations thereof.
 23. Themethod of claim 22, wherein the at least one ethylenically unsaturatedmonomer includes at least one member selected from the group consistingof acrylic acid, maleic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, monomethyl maleate, and salts and combinationsthereof.